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1 Vitreous State Laboratory, The Catholic University of America, 620 Michigan Ave., N.E. Washington D.C. 20064, USA
2 Department of Mineral Sciences, Smithsonian Institution, Washington, D.C. 20560-0119, USA
3 Surface and Microanalysis Science Division, National Institute of Standards and Technology, Gaithersburg, Maryland 20899-0001, USA
* E-mail address of corresponding author: davidm{at}vsl.cua.edu
Lattice dynamic calculations for the sepiolite and palygorskite structures using polarized Raman and FTIR spectra provide a fundamental basis for interpreting spectral features by assigning vibrational modes. The SiO stretch and OSiO bond bending force constants determined for palygorskite are similar to equivalent values calculated previously for other phyllosilicates. The MgO bond stretch values, on the other hand, are about half of those determined for the equivalent AlO and MgO bond stretch environments in other phyllosilicates, suggesting that the bonding within the octahedral ribbons in palygorskite and sepiolite is weaker than that in the continuous octahedral sheets in micas. The weaker bonding allows more flexible octahedral environments in palygorskite and sepiolite, giving rise to higher probabilities for cation substitutions and vacancies relative to the micas. Above ~700 cm1 in the IR and 750 cm1 in the Raman spectra, the eigenmodes are dominated by atomic displacements within the silicate sheets. Below 700 cm1 the eigenmodes become mixed with motions among the Mg octahedra and the silicate sheets; the eigenmodes assigned to the most prominent peaks in the Raman spectra (near 700 cm1) belong to this group. As mode frequencies decrease, the corresponding eigenmodes evolve from more localized Mg-O stretch, O-Mg-O bend and O-Si-O bend motions to longer-range motions such as silicate sheet deformations caused by silicate tetrahedra rotation and silicate sheet shearing around the Mg-octahedral sheets.
Key Words: FTIR Palygorskite Raman Sepiolite
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